Composite laminated ceramic electronic component

ABSTRACT

A composite laminated ceramic electronic component that includes co-fired low dielectric-constant ceramic layers and high dielectric-constant ceramic layers. The low dielectric-constant ceramic layers and the high dielectric-constant ceramic layers are each composed of a glass ceramic containing: a first ceramic composed of MgAl 2 O 4  and/or Mg 2 SiO 4 ; a second ceramic composed of BaO, RE 2 O 3  (where RE is a rare-earth element), and TiO 2 ; glass containing each of 44.0 to 69.0 weight % of RO (where R is an alkaline-earth metal), 14.2 to 30.0 weight % of SiO 2 , 10.0 to 20.0 weight % of B 2 O 3 , 0.5 to 4.0 weight % of Al 2 O 3 , 0.3 to 7.5 weight % of Li 2 O, and 0.1 to 5.5 weight % of MgO; and MnO. The content ratios of the glass, etc. are varied between the low dielectric-constant ceramic layers and the high dielectric-constant ceramic layers.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of International applicationNo. PCT/JP2013/052577, filed Feb. 5, 2013, which claims priority toJapanese Patent Application No. 2012-028179, filed Feb. 13, 2012, theentire contents of each of which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to a laminated ceramic electronic component suchas a multilayer ceramic substrate which has, for example, a microwaveresonator, filter, or capacitor configured therein, and moreparticularly, to a composite laminated ceramic electronic componentincluding a composite structure obtained by stacking lowdielectric-constant ceramic layers with a relatively low relativepermittivity and high dielectric-constant ceramic layers with arelatively high relative permittivity.

BACKGROUND OF THE INVENTION

In recent years, with a reduction in size, weight, and thickness forelectronic devices, the reduction in size has been required forelectronic components for use in electronic devices. However,conventionally, electronic components such as capacitors and resonatorsare each configured separately, and the reduction just in size for thesecomponents thus has limitations in the reduction in size for electronicdevices. Consequently, various multilayer ceramic substrates have beenproposed which have elements, such as capacitors and resonators,configured therein.

In addition, in order to deal with the recent trends of furtherreductions in size and recent higher frequencies for multilayer ceramicsubstrates, various multilayer ceramic substrates has been also proposedwhich have a composite structure in which low dielectric-constantceramic layers and high dielectric-constant ceramic layers are stacked.For example, as described in Japanese Patent Application Laid-Open No.2002-29827 (Patent Document 1) and Japanese Patent Application Laid-OpenNo. 2003-63861 (Patent Document 2), multilayer ceramic substrates havebeen proposed in which high dielectric-constant ceramic layers composedof a high dielectric-constant and low-dielectric-loss material, withelements such as capacitors and resonators configured therein, areplaced so as to be sandwiched by low dielectric-constant ceramic layerswith wiring formed and semiconductor elements mounted.

Patent Document 1 and Patent Document 2 also discloses a glass ceramiccomposition suitable for forming low dielectric-constant ceramic layersor a glass ceramic composition suitable for forming highdielectric-constant ceramic layers.

More specifically, Patent Document 1 discloses, in claim 1 thereof, aglass ceramic composition containing an MgAl₂O₄-based ceramic and glass.More particularly, a glass ceramic composition is described whichcontains: a MgAl₂O₄— based ceramic powder; and a glass powder containing13 to 50 weight % of silicon oxide in terms of SiO₂, 8 to 60 weight % ofboron oxide in terms of B₂O₃, 0 to 20 weight % of aluminum oxide interms of Al₂O₃, and 10 to 55 weight % of magnesium oxide in terms ofMgO.

In addition, Patent Document 1 discloses, in claim 2 thereof, analkaline-earth metal oxide which may be further contained in aproportion of 20 weight % or less, and in claim 6 thereof, the glasscontent which may be preferably 20 to 80 weight % of the total.

The glass ceramic composition described in Patent Document 1 achieves,in the case of a sintered body thereof, a relatively low relativepermittivity such as, for example, 8 or less, and can be thus madesuitable for high-frequency applications.

Next, Patent Document 2 discloses, as a high dielectric-constantmaterial constituting high dielectric-constant ceramic layers with arelatively high relative permittivity, a material containing aBaO—TiO₂—RE₂O₃ (RE is a rare-earth element) dielectric and glass. Theglass contains, according to claim 2 of Patent Document 2, 10 to 25weight % of SiO₂, 10 to 40 weight % of B₂O₃, 25 to 55 weight % of MgO, 0to 20 weight % of ZnO, 0 to 15 weight % of Al₂O₃, 0.5 to 10 weight % ofLi₂O, and 0 to 10 weight % of RO (R is at least one of Ba, Sr, and Ca).In addition, as described in claim 4 of Patent Document 2, the contentof the glass is preferably 15 to 35 weight %.

On the other hand, Patent Document 2 discloses a material similar tothat in Patent Document 1, as a low dielectric-constant materialconstituting the low dielectric-constant ceramic layers.

The inventors have first found insulation reliability to be furtherimproved, as a result of making further experiments on the respectiveglass ceramic compositions described in Patent Documents 1 and 2mentioned above. The cause is assumed as follows.

The glass contained in the glass ceramic composition described in eachof Patent Documents 1 and 2 is indented to allow firing at a temperatureof 1000° C. or lower, but is a composition that is likely to becrystallized. In the case of the glass ceramic compositions described inPatent Documents 1 and 2, the glass component and the ceramic componentreact to deposit crystals in the firing process, and it is thusdifficult to stabilize the crystal quantity and the quantity of theglass component at the time of completion of firing. Further, thisinstability of the crystal quantity and the quantity of the glasscomponent at the time of completion of firing is assumed to decrease theinsulation reliability.

For example, the glass contained in the glass ceramic compositionsdescribed in each of Patent Documents 1 and 2 contains a relativelylarge amount of MgO, this large amount of MgO in the glass is believedto deposit crystals of MgAl₂O₄ and/or Mg₂SiO₄ from the glass component,and this deposition is assumed to lead to a decrease in insulationreliability.

In addition, in particular, the high dielectric-constant materialdescribed in Patent Document 2 requires the addition of glass in orderto allow firing at temperatures of 1000° C. or less, and on the otherhand, requires a BaO—TiO₂—RE₂O₃ based dielectric contained in order toincrease the relative permittivity. However, free Ti ions from theBaO—TiO₂—RE₂O₃ based dielectric cause oxygen defects. Furthermore, theseoxygen defects can cause a decrease in insulation reliability in use at,in particular, high temperature and high voltage for a long period oftime, etc.

In addition, the inventors of the present application have recognized,as a result of repeated experiments, problems of the compositions of therespective glass ceramic compositions described in Patent Documents 1and 2, such as difficulty in stably achieving desired relativepermittivity in a wide range from low relative permittivity to highrelative permittivity.

More specifically, the glass contained in the glass ceramic compositionsdescribed in Patent Documents 1 and 2 is likely to react with theceramic component to be crystallized in the firing process as describedpreviously. When the crystals are deposited, the relative permittivitywill be changed, and it will be thus difficult to achieve desiredrelative permittivity.

In addition, the glass contained in the glass ceramic compositionsdescribed in Patent Documents 1 and 2 fails to have favorablewettability to MgAl₂O₄ based ceramics or BaO—TiO₂—RE₂O₃ baseddielectrics. Therefore, the glass ceramic composition is not able to besintered, unless a relatively large amount of glass is added. However,the large additive amount of glass will decrease the relativepermittivity. Thus, it is difficult to prepare, in particular, highdielectric-constant materials.

Furthermore, as a specific problem with composite laminate ceramicelectronic components, it has to be also considered whether theproperties obtained in the case of a low dielectric-constant ceramiclayer by itself and the properties obtained in the case of a highdielectric-constant ceramic layer by itself are almost maintained in thecase of co-firing low dielectric-constant ceramic layers and highdielectric-constant ceramic layers. In particular, the glass containedin the glass ceramic composition described in each of Patent Documents 1and 2 has a composition that is likely to be crystallized, and thus,from the perspective of difficulty in stabilizing the crystal quantityand the quantity of the glass component at the time of completion offiring, it is assumed that there can be also a good possibility that, asa result of co-firing the low dielectric-constant ceramic layer and thehigh dielectric-constant ceramic layer, the properties of the respectiveceramic layers by themselves will be lost.

-   Patent Document 1: Japanese Patent Application Laid-Open No.    2002-29827-   Patent Document 2: Japanese Patent Application Laid-Open No.    2003-63861

SUMMARY OF THE INVENTION

Therefore, an object of this invention is to provide a compositelaminated ceramic electronic component which can have co-fired lowdielectric-constant ceramic layers and high dielectric-constant ceramiclayers, and achieve reasonable characteristics for each of the lowdielectric-constant ceramic layers and high dielectric-constant ceramiclayers.

This invention is directed to a composite laminated ceramic electroniccomponent including a low dielectric-constant ceramic layer and a highdielectric-constant ceramic layer that are stacked, andcharacteristically configured as follows in order to solve the technicalproblems mentioned above.

The low dielectric-constant ceramic layer and high dielectric-constantceramic layer each include a glass ceramic containing: (1) a firstceramic including at least one of MgAl₂O₄ and Mg₂SiO₄; (2) a secondceramic including BaO, RE₂O₃ (RE is a rare-earth element), and TiO₂; (3)glass containing each of 44.0 to 69.0 weight % of RO (R is at least onealkali-earth metal selected from Ba, Ca, and Sr), 14.2 to 30.0 weight %of SiO₂, 10.0 to 20.0 weight % of B₂O₃, 0.5 to 4.0 weight % of Al₂O₃,0.3 to 7.5 weight % of Li₂O, and 0.1 to 5.5 weight % of MgO; and (4)MnO.

Further, the low dielectric-constant ceramic layer contains 47.55 to69.32 weight % of the first ceramic, contains 6 to 20 weight % of theglass, contains 7.5 to 18.5 weight % of MnO, and contains, as the secondceramic, each of: 0.38 to 1.43 weight % of BaO; 1.33 to 9.5 weight % ofRE₂O₃; and 0.95 to 6.75 weight % of TiO₂, and has a relativepermittivity of 15 or less.

On the other hand, the high dielectric-constant ceramic layer contains15.5 to 47 weight % of the first ceramic, contains 7 to 20 weight % ofthe glass, contains 5.5 to 20.5 weight % of the MnO, contains, as thesecond ceramic, each of: 2.1 to 5.2 weight % of BaO; 13.2 to 34.75weight % of RE₂O₃; and 9.5 to 24.75 weight % of TiO₂, and has a relativepermittivity of 20 or more and 25 or less.

Preferably, the content G_(L) of the glass contained in the lowdielectric-constant ceramic layer and the content G_(H) of the glasscontained in the high dielectric-constant ceramic layer are adapted tomeet the condition of 0.74≦G_(L)/G_(H)≦1.76. As can be seen from theexperimental examples described later, when this condition is met, theinsulation reliability of, in particular, the low dielectric-constantceramic layer can be improved.

Furthermore, preferably, the content M_(L) of the MnO contained in thelow dielectric-constant ceramic layer and the content M_(H) of the MnOcontained in the high dielectric-constant ceramic layer are adapted tomeet the condition of 0.7≦M_(L)/M_(H)≦1.95. As can be seen from theexperimental examples described later, when this condition is met, theinsulation reliability of, in particular, the high dielectric-constantceramic layer can be improved.

More preferably, the two conditions mentioned above are both adapted tobe met. Thus, as can be seen from the experimental examples describedlater, the insulation reliability can be further improved for both thelow dielectric-constant ceramic layer and the high dielectric-constantceramic layer.

Furthermore, the low dielectric-constant ceramic layer preferablyfurther contains 3 to 20 weight % of a third ceramic including at leastone of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈. Thus, as can be seen from theexperimental examples described later, warpage can be made less likelyto be caused in the composite laminate ceramic electronic component.

In the case mentioned above, more preferably, the highdielectric-constant ceramic layer contains 1 to 7.5 weight % of thethird ceramic, and the difference (C_(L)−C_(H)) is 2.5 weight % or morebetween the content C_(L) of the third ceramic contained in the lowdielectric-constant ceramic layer and the content C_(H) of the thirdceramic contained in the high dielectric-constant layer. This differencecan, in the composite laminated ceramic electronic component, makewarpage more unlikely to be caused, and achieve high insulationreliability equivalent to that in the case of the highdielectric-constant ceramic layer or low dielectric-constant ceramiclayer alone containing no third ceramic, without being affected bycontaining the third ceramic.

The low dielectric-constant ceramic layer may further contain 0.23weight % or less of CuO, and the high dielectric-constant ceramic layermay further contain 1.2 weight % or less of CuO.

According to this invention, the low dielectric-constant ceramic layerand the high dielectric-constant ceramic layer can be subjected toco-sintering without any difficulty, because the low dielectric-constantceramic layer and the high dielectric-constant ceramic layer arecomposed of the glass ceramic containing the common elements.

In addition, the insulation reliability can be increased, because thelow dielectric-constant ceramic layer and the high dielectric-constantceramic layer each contain therein the glass which is less likely to becrystallized, and contain MnO.

Furthermore, the low dielectric-constant ceramic layer can achievecharacteristics such as a relative permittivity of 15 or less, highinsulation reliability, a large value for Qf, and a temperaturecoefficient of capacitance (TCC) of 150 ppm/K or less in terms ofabsolute value.

On the other hand, the high dielectric-constant ceramic layer canachieve characteristics such as a relative permittivity of 20 or moreand 25 or less, high insulation reliability, a large value for Qf, and atemperature coefficient of capacitance (TCC) of 60 ppm/K or less interms of absolute value.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 is a cross-sectional view illustrating a ceramic multilayermodule 1 including a multilayer ceramic substrate 2 as an example of acomposite laminated ceramic electronic component according to thisinvention.

FIG. 2 is a perspective view illustrating the ceramic multilayer module1 shown in FIG. 1 in an exploded form.

FIG. 3 is a perspective view illustrating the appearance of an LC filter21 as another example of a composite laminated ceramic electroniccomponent according to this invention.

FIG. 4 is an equivalent circuit diagram given by the LC filter 21 shownin FIG. 3.

FIG. 5 is a perspective view illustrating, in an exploded form, acomponent main body 23 included in the LC filter 21 shown in FIG. 3.

FIGS. 6(A) and 6(B) are cross-sectional views illustrating two types ofco-sintered bodies prepared in experimental examples.

DETAILED DESCRIPTION OF THE INVENTION

A ceramic multilayer module 1 including a multilayer ceramic substrate 2as an example of a composite laminated ceramic electronic componentaccording to this invention will be described with reference to FIGS. 1and 2.

The multilayer ceramic substrate 2 included in the ceramic multilayermodule 1 includes a plurality of low dielectric-constant ceramic layers3 and a plurality of high dielectric-constant ceramic layers 4 that arestacked, the plurality of low dielectric-constant ceramic layers 3 islocated to sandwich the plurality of high dielectric-constant ceramiclayers 4, and these layers are co-fired.

The low dielectric-constant ceramic layers 3 and the highdielectric-constant ceramic layers 4 are each composed of a glassceramic including:

(1) a first ceramic composed of at least one of MgAl₂O₄ and Mg₂SiO₄;

(2) a second ceramic composed of BaO, RE₂O₃ (RE is a rare-earthelement), and TiO₂;

(3) glass containing each of 44.0 to 69.0 weight % of RO (R is at leastone alkali-earth metal selected from Ba, Ca, and Sr), 14.2 to 30.0weight % of SiO₂, 10.0 to 20.0 weight % of B₂O₃, 0.5 to 4.0 weight % ofAl₂O₃, 0.3 to 7.5 weight % of Li₂O, and 0.1 to 5.5 weight % of MgO; and

(4) MnO.

The low dielectric-constant ceramic layers 3 and the highdielectric-constant ceramic layers 4 can be subjected to co-sinteringwithout any difficulty, because the low dielectric-constant ceramiclayers 3 and the high dielectric-constant ceramic layers 4 are composedof the glass ceramic containing the common elements as just describedabove.

Furthermore, the above-described glass ceramic for use in this inventionachieves the following effects as will become clear from theexperimental examples described later.

(A) The insulation reliability is high.

The glass contained in the glass ceramic has a composition which is lesslikely to be crystallized. Therefore, the crystal quantity and the glasscomponent quantity are stabilized at the time of completion of firing,and the insulation reliability can be thus improved. This is because, ascompared with the glass contained in what is described in PatentDocuments 1 and 2, the glass can inhibit deposition of crystals such asMgAl₂O₄ and Mg₂SiO₄ due to the lower MgO content, and moreover, with theincreased RO content, provide a composition that is not crystallized.

In addition, the glass ceramic composition contains MnO. No MnO iscontained in what is described in Patent Documents 1 and 2. Ti ionsproduced by the reduction of the Ti oxide can cause oxygen defects,thereby causing a decrease in insulation reliability in use at hightemperature and high voltage for a long period of time, etc. In thisinvention, the substitution of Mn for the Ti site inhibits thegeneration of oxygen defects. This is also assumed to contribute toimproved insulation reliability.

(B) Products with a desired relative permittivity can be easily achievedover a wide range from low relative permittivity to high relativepermittivity.

As described previously, the glass described in Patent Documents 1 and 2is likely to be crystallized by reaction with the ceramic component, andthus likely to undergo a change in relative permittivity. In contrast,the glass contained in the glass ceramic for use in this invention isless likely to be crystallized, and it is thus easy to manufactureproducts with a desired relative permittivity.

In addition, the glass contained in the glass ceramic for use in thisinvention is glass that is high in wettability relative to, and low inreactivity with the first ceramic and the second ceramic. Accordingly,the glass ceramic is able to be sintered even when the glass componentis reduced, and less likely to develop a reaction and stable even whenthe glass component is increased reversely. Therefore, it is possible towidely adjust the respective contents of the ceramic component and glasscomponent in the glass ceramic, and thus, a wide range of products fromlow dielectric-constant products to high dielectric-constant productscan be easily provided just by adjusting the respective contents of theceramic component and glass component. More specifically, glass ceramicssuitable for constituting the low dielectric-constant ceramic layers 3and glass ceramics suitable for constituting the highdielectric-constant ceramic layers 4 can be provided as described below.

It is to be noted that the glass ceramic for use in this invention willnot vary significantly in composition between before and after firing.Although the B₂O₃ and Li₂O in the glass may volatilize during firing insome cases, even in those cases, the proportions of

other constituents after the firing are almost unchanged from thosebefore the firing.

The glass ceramic constituting the low dielectric-constant ceramiclayers 3 contains 47.55 to 69.32 weight % of the first ceramic, contains6 to 20 weight % of the glass, contains 7.5 to 18.5 weight % of MnO, andcontains, as the second ceramic, each of: 0.38 to 1.43 weight % of BaO;1.33 to 9.5 weight % of RE₂O₃; and 0.95 to 6.75 weight % of TiO₂.

The low dielectric-constant ceramic layers 3 can achieve characteristicssuch as a relative permittivity of 15 or less, high insulationreliability, a large value for Qf, and a temperature coefficient ofcapacitance (TCC) of 150 ppm/K or less in terms of absolute value.

On the other hand, the glass ceramic constituting the highdielectric-constant ceramic layers 4 contains 15.5 to 47 weight % of thefirst ceramic, contains 7 to 20 weight % of the glass, contains 5.5 to20.5 weight % of the MnO, and contains, as the second ceramic, each of:2.1 to 5.2 weight % of BaO; 13.2 to 34.75 weight % of RE₂O₃; and 9.5 to24.75 weight % of TiO₂.

The high dielectric-constant ceramic layers 4 can achievecharacteristics such as a relative permittivity of 20 or more and 25 orless, high insulation reliability, a large value for Qf, and atemperature coefficient of capacitance (TCC) of 60 ppm/K or less interms of absolute value.

Preferably, the content G_(L) of the glass contained in the lowdielectric-constant ceramic layers 3 and the content G_(H) of the glasscontained in the high dielectric-constant ceramic layers 4 are adaptedto meet the condition of 0.74≦G_(L)/G_(H)≦1.76. As can be seen from theexperimental examples described later, when this condition is met, theinsulation reliability of, in particular, the low dielectric-constantceramic layers 3 can be improved. This is assumed to be becauseinterdiffusion can be inhibited between the glass component in the lowdielectric-constant ceramic layers 3 and the glass component in the highdielectric-constant ceramic layers 4.

Furthermore, preferably, the content M_(L) of the MnO contained in thelow dielectric-constant ceramic layers 3 and the content M_(H) of theMnO contained in the high dielectric-constant ceramic layers 4 areadapted to meet the condition of 0.7≦M_(L)/M_(H)≦1.95. As can be seenfrom the experimental examples described later, when this condition ismet, the insulation reliability of, in particular, the highdielectric-constant ceramic layers 4 can be improved. This is assumed tobe because interdiffusion can be inhibited between the MnO component inthe low dielectric-constant ceramic layers 3 and the MnO component inthe high dielectric-constant ceramic layers 4.

More preferably, the two conditions mentioned above are both adapted tobe met. Thus, as can be seen from the experimental examples describedlater, the insulation reliability can be further improved for both thelow dielectric-constant ceramic layers 3 and the highdielectric-constant ceramic layers 4.

Furthermore, the low dielectric-constant ceramic layers 3 preferablyfurther contain 3 to 20 weight % of a third ceramic including at leastone of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈. Thus, as can be seen from theexperimental examples described later, warpage can be made less likelyto be caused in the multilayer ceramic substrate 2.

In the case mentioned above, more preferably, the highdielectric-constant ceramic layers 4 also contain 1 to 7.5 weight % ofthe third ceramic, and the difference (C_(L)−C_(H)) is 2.5 weight % ormore between the content C_(L) of the third ceramic contained in the lowdielectric-constant ceramic layer and the content C_(H) of the thirdceramic contained in the high dielectric-constant layer. This differencecan, in the multi-layer ceramic substrate 2, make warpage more unlikelyto be caused, and achieve high insulation reliability equivalent to thatin the case of the high dielectric-constant ceramic layers 4 alone orlow dielectric-constant ceramic layers 3 alone of composition containingno third ceramic.

The low dielectric-constant ceramic layers 3 may further contain 0.23weight % or less of CuO, and the high dielectric-constant ceramic layers4 may further contain 1.2 weight % or less of CuO.

The multilayer ceramic substrate 2 includes various wiring conductors.The wiring conductors typically include internal conductor films 6formed along specific interfaces between the ceramic layers 3 and 4, viahole conductors 7 extending so as to pass through specific ones of theceramic layers 3 and 4, and external conductor films 8 formed on theouter surface of the multilayer ceramic substrate 2.

Some of the internal conductor films 6 mentioned above, which areprovided in conjunction with the high dielectric-constant ceramic layers4, are placed so as to provide electrostatic capacitance, therebyconstituting capacitor elements.

The upper surface of the multilayer ceramic substrate 2 is mounted withmultiple electronic components 9 to 17. Among the electronic components9 to 17 shown, for example, the electronic component 9 is a diode, theelectronic component 11 is a laminated ceramic capacitor, and theelectronic component 16 is a semiconductor IC. These electroniccomponents 9 to 17 electrically connected to specific ones of theexternal conductor films 8 formed on the upper surface of the multilayerceramic substrate 2 constitute circuits required for the ceramicmultilayer module 1, along with the wiring conductors formed within themultilayer ceramic substrate 2.

The upper surface of the multilayer ceramic substrate 2 has a conductivecap 18 fixed thereon for shielding the electronic components 9 to 17.The conductive cap 18 is electrically connected to specific ones of thevia hole conductors 7 mentioned previously.

In addition, the ceramic multilayer module 1 is mounted on a motherboard, not shown, with the use of, as connecting terminals, specificones of the external conductor films 8 formed on the lower surface ofthe multilayer ceramic substrate 2.

The multilayer ceramic substrate 2 can be produced with the use of knownco-firing techniques for ceramic laminates.

Specifically, first, ceramic green sheets are prepared for the lowdielectric-constant ceramic layers 3. More specifically, ceramic slurryis obtained by adding an organic vehicle composed of a binder resin anda solvent to a raw material composition for providing the glass ceramicdescribed above. This ceramic slurry is formed into the shape of a sheetby, for example, a doctor blade method, dried, and then subjected topunching into a predetermined size, thereby providing ceramic greensheets. Then, in order to form wiring conductors, these ceramic greensheets are provided with a conductive paste containing, for example,copper or silver as its main constituent in a desired pattern.

On the other hand, ceramic green sheets including a raw materialcomposition for providing the glass ceramic constituting the highdielectric-constant ceramic layers 4 are prepared by the same method asin the case of the ceramic green sheets for the low dielectric-constantceramic layers 3. Then, in order to form wiring conductors, theseceramic green sheets are provided with a conductive paste containing,for example, copper or silver as its main constituent in a desiredpattern.

Next, the ceramic green sheets for the low dielectric-constant ceramiclayers 3 and the ceramic green sheets for the high dielectric-constantceramic layers 4, which are obtained in the way described above, areeach stacked in a predetermined order for a predetermined number oflayers, and then pressurized in the thickness direction.

Next, the raw stacked body obtained in the way described above issubjected to firing at a temperature of 1000° C. or lower, for example,800 to 1000° C., thereby making it possible to provide the multilayerceramic substrate 2. In this case, the firing is carried out in anon-oxidizing atmosphere such as a nitrogen atmosphere when the wiringconductors contain copper as their main constituent, or carried out inan oxidizing atmosphere such as the atmosphere when the conductorscontain silver as their main constituent.

Next, soldering or the like is applied to mount the electroniccomponents 9 to 17 and attach the conductive cap 18 on the surface ofthe multilayer ceramic substrate 2, thereby completing the ceramicmultilayer module 1.

The ceramic multilayer module 1 described above can be made suitable forhigh-frequency applications, and excellent in reliability, because thelow dielectric-constant ceramic layers 3 included in the multilayerceramic substrate 2 have a relative permittivity of 15 or less, a largevalue for Qf, and a temperature coefficient of capacitance (TCC) of 150ppm/K or less in terms of absolute value, whereas the highdielectric-constant ceramic layers 4 therein have a relativepermittivity of 20 or more and 25 or less, a large value for Qf, and atemperature coefficient of capacitance (TCC) of 60 ppm/K or less interms of absolute value. In addition, the ceramic multilayer module 1can be improved in insulation reliability.

Next, with reference to FIGS. 3 through 5, an LC filter 21 will bedescribed as another example of a composite laminated ceramic electroniccomponent according to this invention.

The LC filter 21 includes, as shown in FIG. 3, a component main body 23as a stacked structure in which a plurality of glass ceramic layers arestacked, respective ends on the outer surface of the component main body23 are provided with terminal electrodes 24 and 25, and middle portionsof respective side surfaces are provided with terminal electrodes 26 and27.

The LC filter 21 is intended to constitute, as shown in FIG. 4, twoinductances L1 and L2 connected in series between the terminalelectrodes 24 and 25, and constitute capacitance C between theconnecting point of the inductances L1 and L2 and the terminalelectrodes 26 and 27.

As shown in FIG. 5, the component main body 23 includes multiple ceramiclayers 28 to 40 that are stacked. It is to be noted that the number ofceramic layers that are stacked is not limited to the number shown.

The ceramic layers 28 to 40 are each obtained in such a way that anorganic vehicle composed of a binder resin and a solvent is added to andmixed with a raw composition for providing the glass ceramic to obtainceramic slurry, the ceramic slurry is formed into the shape of a sheetby a doctor blade method, dried, and then subjected to punching into apredetermined size to obtain ceramic green sheets, and the ceramic greensheets are subjected to firing.

In addition, in order to provide the inductances L1 and L2 as well asthe capacitance C as shown in FIG. 4, wiring conductors are provided inthe following manner, in conjunction with specific ones of the ceramiclayers 28 to 40.

On the ceramic layer 30, a coil pattern 41 is formed which constitutes apart of the inductance L1, and an extraction pattern 42 is formed whichextends from one end of the coil pattern 41, and the other end of thecoil pattern 41 is provided with a via hole conductor 43. The extractionpattern 42 is connected to the terminal electrode 24.

On the ceramic layer 31, a coil pattern 44 is formed which constitutes apart of the inductance L1, and one end of the pattern is provided with avia hole conductor 45. The other end of the coil pattern 44 is connectedto the via hole conductor 43 mentioned previously.

The ceramic layer 32 is provided with a via hole conductor 46 connectedto the via hole conductor 45 mentioned above.

On the ceramic layer 33, a capacitor pattern 47 is formed whichconstitutes a part of the capacitance C, and extraction patterns 48 and49 are formed which extend from the capacitor pattern 47. The extractionpatterns 48 and 49 are connected to the terminal electrodes 26 and 27.In addition, the ceramic layer 33 is provided with a via hole conductor50 connected to the via hole conductor 46 mentioned previously.

On the ceramic layer 34, a capacitor pattern 51 is formed whichconstitutes a part of the capacitance C, and a via hole conductor 52 isprovided which is connected to the capacitor pattern 51. The capacitorpattern 51 is connected to the via hole conductor 50 mentionedpreviously.

On the ceramic layer 35, a capacitor pattern 53 is formed whichconstitutes a part of the capacitance C, and extraction patterns 54 and55 are formed which extend from the capacitor pattern 53. The extractionpatterns 54 and 55 are connected to the terminal electrodes 26 and 27.In addition, the ceramic layer 35 is provided with a via hole conductor56 connected to the via hole conductor 52 mentioned previously.

The ceramic layer 36 is provided with a via hole conductor 57 connectedto the via hole conductor 56 mentioned above.

On the ceramic layer 37, a coil pattern 58 is formed which constitutes apart of the inductance L2, and one end of the pattern is provided with avia hole conductor 59. The other end of the coil pattern 58 is connectedto the via hole conductor 57 mentioned previously.

On the ceramic layer 38, a coil pattern 60 is formed which constitutes apart of the inductance L2, and an extraction pattern 61 is formed whichextends from one end of the coil pattern 60. The extraction pattern 61is connected to the terminal electrode 25. The other end of the coilpattern 60 is connected to the via hole conductor 59 mentionedpreviously.

For the formation of the coil patterns 41, 44, 58, and 60, extractionpatterns 42, 48, 49, 54, 55, and 61, via hole conductors 43, 45, 46, 50,52, 56, 57, and 59, as well as capacitor patters 47, 51, and 53 aswiring conductors as mentioned above, a conductive paste is used whichcontains, for example, copper or silver as its main constituent, and forthe application of the conductive paste, for example, screen printing isapplied.

Then, in order to obtain the component main body 23, the ceramic greensheets to serve as each of the ceramic layers 28 to 40 mentioned aboveare stacked in a predetermined order, pressurized in the thicknessdirection, and then subjected to firing at a temperature of 1000° C. orlower, for example, 800 to 1000° C. In this case, as in the case of theceramic multilayer module 1 described previously, the firing is carriedout in a non-oxidizing atmosphere such as a nitrogen atmosphere when thewiring conductors contain copper as their main constituent, or carriedout in an oxidizing atmosphere such as the atmosphere when theconductors contain silver as its main constituent.

Furthermore, for the formation of the terminal electrodes 24 to 27 onthe outer surface of the component main body 23, a thin-film formationmethod or the like such as vapor deposition, plating, or sputtering isapplied, or application and baking with a conductive paste containing,for example, copper or silver as its main constituent, is also applied.

In the LC filter 21 described above, among the ceramic layers 28 to 40,the ceramic layers 33 and 34 which directly contribute to, inparticular, the composition of the capacitance C are composed of thesame high dielectric-constant ceramic material as that constituting thehigh dielectric-constant ceramic layers 4 included in the ceramicmultilayer module 1 shown in FIG. 1 as described previously, whereas theother ceramic layers 28 to 32 and 35 to 40 are composed of the same lowdielectric-constant ceramic material as that constituting the lowdielectric-constant ceramic layers 3 included in the ceramic multilayermodule 1.

This invention can be also applied to composite laminated ceramicelectronic components, besides the ceramic multilayer module 1 or LCfilter 21 as shown.

Next, experimental examples will be described which were implemented forevaluating characteristics achieved by the glass ceramic for use in thisinvention and evaluating characteristics provided by composite laminatedceramic electronic components configured with the use of the glassceramic.

[Preparation of Glass]

First, as glass contained in the glass ceramic, and used in common inthe following experimental examples, compositions prepared as shown inTable 1 were melted at a temperature of 1100 to 1400° C., vitrified byrapid cooling, and then subjected to wet grinding to prepare glasspowders of various compositions.

TABLE 1 Total of Alkali - Glass Li₂O BaO SrO CaO MgO SiO₂ B₂O₃ Al₂O₃Earth Metal Number (weight %) (weight %) (weight %) (weight %) (weight%) (weight %) (weight %) (weight %) (weight %) G1 0.2 45 6.5 2.5 0.528.2 15.1 2 54 G2 0.3 45 6.5 2.5 0.5 27.7 15.5 2 54 G3 2 45 6.5 2.5 0.526.5 15 2 54 G4 7.5 43.5 6 2 0.5 24 14.5 2 51.5 G5 8 43 6 2 0.5 23.5 152 51 G6 2.6 28 12.9 4 0.5 30 20 2 44.9 G7 2.6 46.5 8 0.4 0.5 25.2 14.8 254.9 G8 3.2 31.4 3.8 2.3 5.5 29.8 20 4 37.5 G9 2.6 30 15 3.3 5.5 24.6 172 48.3 G10 2.6 49 7.9 2.5 0.5 20.5 15 2 59.4 G11 2.6 57 6.2 2.5 0.5 18.810.4 2 65.7 G12 2.6 60 6.4 2.5 0.8 15 10.7 2 68.9 G13 2.6 48.9 15.8 4.80.5 14.6 10.8 2 69.5 G14 2.6 46.8 18.5 3.7 0.5 14.8 11.1 2 69 G15 2.646.7 8.5 4.5 0.5 26.2 9 2 59.7 G16 2.6 45 9 2.5 0.1 25.5 13.3 2 56.5 G172.6 42 5.4 2.5 0.5 32 13 2 49.9 G18 2.6 44.5 1.6 4.4 0.8 24.3 19.8 250.5 G19 2.6 41.4 6.5 2 0.5 23.5 21.5 2 49.9 G20 2.6 44 3.5 2.5 0.1 24.718.6 4 50 G21 2.6 43.7 5 3.5 4 23.3 17.4 0.5 52.2 G22 2.6 47 6.5 2.5 0.523.4 15 2.5 56 G23 2.6 35.8 7.7 0.5 4 27.6 18.8 3 44 G24 2.6 44.7 6 52.5 22 15 2.2 55.7 G25 2.6 46.9 1 2.8 0.8 27.6 16.3 2 50.7 G26 2.6 40.220 2.5 0.5 19.8 12.4 2 62.7 G27 2.6 44.9 6 2 0.5 30 12 2 52.9 G28 2.645.5 11.8 3.8 0.5 14.2 18.8 2.8 61.1 G29 2.6 45.4 7.5 3.5 0.5 28.5 10 256.4 G30 2.6 45.2 7.1 3.1 0.5 19.5 20 2 55.4 G31 2.6 46.5 6.7 5.5 0.522.8 13.4 2 58.7 G32 2.6 45 6.7 2.7 0 25.5 15.5 2 54.4 G33 2.6 43.6 6.32.2 6.5 22.2 14.6 2 52.1 G34 2.6 43.8 11.2 4.7 4.8 11.4 19.5 2 59.7 G352.6 46.4 7.8 3.9 0.5 24.5 14 0.3 58.1 G36 2.6 45 6.5 2.5 0.5 24.4 13.5 554

Experimental Example 1

In Experimental Example 1, evaluations were made on glass ceramics alonefor low dielectric-constant ceramic layers.

First, as the first ceramic, MgCO₃ and Al₂O₃ were blended inpredetermined proportions, and subjected to calcination and wet grindingto prepare a spinel compound: MgAl₂O₄, and MgCO₃ and SiO₂ were blendedin predetermined proportions, and subjected to calcination and wetgrinding to prepare a forsterite compound: Mg₂SiO₄.

Next, so as to provide the compositions shown in Tables 2 and 3, therespective powders of the glass shown in Table 1, MgAl₂O₄, Mg₂SiO₄, BaO,TiO₂, Nd₂O₃ and Sm₂O₃ as RE₂O₃, MnO, and CuO were blended and mixed, andan organic solvent and a binder were then added thereto to prepareslurry.

TABLE 2 Second Ceramic First Ceramic (weight %) Sample Glass (weight %)RE₂O₃ MnO CuO Number Number (weight %) MgAl₂O₄ Mg₂SiO₄ Bao TiO₂ Nd₂O₃Sm₂O₃ (weight %) (weight %) 1 G1 13 0 61.92 0.8 3.8 5.4 0 15 0.08 2 G113 61.92 0 0.8 3.8 5.4 0 15 0.08 3 G2 13 0 61.92 0.8 3.8 5.4 0 15 0.08 4G3 13 0 61.92 0.8 3.8 5.4 0 15 0.08 5 G4 13 0 61.92 0.8 3.8 5.4 0 150.08 6 G5 13 0 61.92 0.8 3.8 5.4 0 15 0.08 7 G5 13 61.92 0 0.8 3.8 5.4 015 0.08 8 G6 13 0 61.92 0.8 3.8 5.4 0 15 0.08 9 G6 13 61.92 0 0.8 3.85.4 0 15 0.08 10 G7 13 0 61.92 0.8 3.8 5.4 0 15 0.08 11 G8 13 0 61.920.8 3.8 5.4 0 15 0.08 12 G8 13 61.92 0 0.8 3.8 5.4 0 15 0.08 13 G9 13 061.92 0.8 3.8 5.4 0 15 0.08 14 G9 13 61.92 0 0.8 3.8 5.4 0 15 0.08 15G10 13 0 61.92 0.8 3.8 5.4 0 15 0.08 16 G11 13 0 61.92 0.8 3.8 5.4 0 150.08 17 G12 13 0 61.92 0.8 3.8 5.4 0 15 0.08 18 G13 13 0 61.92 0.8 3.85.4 0 15 0.08 19 G14 13 0 61.92 0.8 3.8 5.4 0 15 0.08 20 G15 13 0 61.920.8 3.8 5.4 0 15 0.08 21 G16 13 0 61.92 0.8 3.8 5.4 0 15 0.08 22 G17 130 61.92 0.8 3.8 5.4 0 15 0.08 23 G18 13 0 61.92 0.8 3.8 5.4 0 15 0.08 24G19 13 0 61.92 0.8 3.8 5.4 0 15 0.08 25 G20 13 0 61.92 0.8 3.8 5.4 0 150.08 26 G21 13 0 61.92 0.8 3.8 5.4 0 15 0.08 27 G22 13 0 61.92 0.8 3.85.4 0 15 0.08 28 G22 13 61.92 61.92 0.8 3.8 5.4 0 15 0.08 29 G23 13 0 00.8 3.8 5.4 0 15 0.08 30 G23 13 61.92 61.92 0.8 3.8 5.4 0 15 0.08 31 G2413 0 0 0.8 3.8 5.4 0 15 0.08 32 G25 13 0 61.92 0.8 3.8 5.4 0 15 0.08 33G26 13 0 61.92 0.8 3.8 5.4 0 15 0.08 34 G27 13 0 61.92 0.8 3.8 5.4 0 150.08 35 G28 13 0 61.92 0.8 3.8 5.4 0 15 0.08 36 G29 13 0 61.92 0.8 3.85.4 0 15 0.08 37 G30 13 0 61.92 0.8 3.8 5.4 0 15 0.08 38 G31 13 0 61.920.8 3.8 5.4 0 15 0.08 39 G32 13 0 61.92 0.8 3.8 5.4 0 15 0.08 40 G32 1361.92 0 0.8 3.8 5.4 0 15 0.08 41 G33 13 0 61.92 0.8 3.8 5.4 0 15 0.08 42G33 13 61.92 0 0.8 3.8 5.4 0 15 0.08 43 G34 13 0 61.92 0.8 3.8 5.4 0 150.08 44 G34 13 61.92 0 0.8 3.8 5.4 0 15 0.08 45 G35 13 0 61.92 0.8 3.85.4 0 15 0.08 46 G35 13 61.92 0 0.8 3.8 5.4 0 15 0.08 47 G36 13 0 61.920.8 3.8 5.4 0 15 0.08 48 G36 13 61.92 0 0.8 3.8 5.4 0 15 0.08

TABLE 3 Second Ceramic First Ceramic (weight %) Sample Glass (weight %)RE₂O₃ MnO CuO Number Number (weight %) MgAl₂O₄ Mg₂SiO₄ BaO TiO₂ Nd₂O₃Sm₂O₃ (weight %) (weight %) 49 G22 15 0 64.92 0.35 1.9 2.75 0 15 0.08 50G22 17 0 68.12 0.8 3.5 6 0 4.5 0.08 51 G22 12 0 69.32 0.38 2 2.75 0 13.50.05 52 G22 15 0 64.4 0.6 3.5 4.5 0 12 0 53 G22 15 63.45 0 0.75 3.5 5.250 12 0.05 54 G22 5 0 59.42 1.4 6.6 9.5 0 18 0.08 55 G22 12 0 60.42 1.46.6 9.5 0 10 0.08 56 G22 12 52.75 14.4 0.75 3.45 4.55 0 12 0.1 57 G22 120 69.55 0.52 2.63 4.27 0 11 0.03 58 G22 15.5 0 63.5 0.4 0.9 1.5 0 18 0.259 G22 13 0 61.92 0.8 3.8 5.4 0 15 0.08 60 G22 10 0 62.13 1.42 6.75 9.50 10 0.2 61 G22 19 0 63.24 0.4 0.95 1.33 0 15 0.08 62 G22 20 0 57.17 0.41.8 2.6 0 18 0.03 63 G22 13 61.92 0 0.8 3.8 5.4 0 15 0.08 64 G22 6 061.55 1.4 6.5 9.5 0 15 0.05 65 G22 14 0 68.42 0.8 3.8 0 5.4 7.5 0.08 66G22 13 0 61.92 0.8 3.8 0 5.4 15 0.08 67 G22 14 60.92 0 0.8 3.8 0 5.4 150.08 68 G22 17 0 47.55 1.405 6.575 9.265 0 18 0.205 69 G22 12.5 0 61.7051.415 6.7 10 0 7.5 0.18 70 G22 12.5 0 60.32 1.43 6.7 9.45 0 9.5 0.1 71G22 15.5 0 60.15 1.2 5.65 7.77 0 9.5 0.23 72 G22 11.75 0 61.87 1.5 6.79.25 0 8.85 0.08 73 G22 20.5 0 60.37 0.75 3.35 4.45 0 10.5 0.08 74 G2210.75 0 61.38 1.42 6.75 0 9.5 10 0.2 75 G22 19 63.24 0 0.4 0.95 0 1.3315 0.08 76 G22 10.5 0 60.495 1.425 6.8 9.45 0 11.25 0.08 77 G22 10 061.2 0.75 3.5 4.5 0 20 0.05 78 G22 12 0 61.35 1.35 6.25 8.75 0 10 0.3 79G22 12.45 69.32 0 0.39 2.125 2.815 0 12.85 0.05 80 G22 16.81 47.55 01.405 6.575 9.265 0 18.2 0.195 81 G22 11.55 0 60.27 0.75 3.6 5.25 0 18.50.08 82 G22 16.8 0 61.55 1.43 0.97 1.3 0 17.9 0.05 83 G22 16.55 0 47.51.415 6.725 9.45 0 18.18 0.18 84 G22 12 69.5 0 0.5 2.7 4.25 0 11 0.05 85G22 16.55 47.455 0 1.415 6.75 9.45 0 18.2 0.18 86 G22 10.5 0 61.7 1.426.7 0 10 9.5 0.18 87 G22 16.8 0 62.58 0.4 0.97 0 1.3 17.9 0.05

Next, the slurry was formed into the shape of a sheet by a doctor blademethod, and dried to obtain ceramic green sheets. The ceramic greensheets were used to appropriately prepare samples, and the samples wereevaluated for relative permittivity (ε_(r)), Qf, temperature coefficientof capacitance (β), and insulation reliability as shown in Tables 4 and5.

More specifically, for the measurement of the ε_(r) and Qf, the ceramicgreen sheets were cut, stacked, and subjected to pressure bonding toprepare pressure-bonded bodies of 0.6 mm×50 mm×50 mm in dimensions.These bodies were subjected to firing at a temperature of 990° C. toobtain ceramic substrates as the samples. These ceramic substrates wereused to measure the ε_(r) and Qf by a cavity resonator method. In thiscase, the measurement frequency was adjusted to approximately 25 GHz.

This experimental example was intended to obtain dielectric materialswith the ε_(r) of 15 or less. The samples of less than 5000 in terms ofQf were determined as rejected articles.

For the measurement of β and the evaluation of the insulationreliability, after cutting the ceramic green sheets, a conductive pastecontaining Cu was printed on the ceramic green sheets in order to forminternal electrodes, and thereafter, laminated ceramic capacitors as thesamples were obtained through respective steps of stacking, pressurebonding, firing, and formation of external electrodes. In the laminatedceramic capacitors, the distance between adjacent internal electrodeswas 10 μm, and the overlapped electrode area was 4 mm□.

Then, for the laminated ceramic capacitors, the electrostaticcapacitance was measured in the range of −40° C. to 85° C. to figure outthe temperature coefficient of capacitance β with 20° C. as a standard.The samples with β in excess of 150 ppm/K in terms of absolute valuewere determined as rejected articles.

Furthermore, for the laminated ceramic capacitors, the insulationresistance was measured after a test of applying DC 200 V for 100 hoursunder a temperature of 150° C., and the samples were determined asrejected articles when the log (IR [Ω]) after this test was less than11, and are shown as “x” in the columns “Insulation Reliability” ofTables 4 and 5, whereas the samples were determined as accepted articleswhen the log (IR [Ω]) was 11 or more, and are shown as “o” in thecolumns “Insulation Reliability” of Tables 4 and 5.

It is to be noted that the insufficiently sintered samples are shown as“Unsintered” in the columns “Remarks” of Tables 4 and 5, and the sampleswith the glass unvitrified are shown as “Unvitrified” in the columns“Remarks”, and these samples were not evaluated for each of ε_(r), Qf,β, and insulation reliability. In addition, rejection reasons for thesamples regarded as rejected articles in this experimental example arebriefly described in the columns of “Remarks”.

TABLE 4 Sample Qf β Insulation Number εr (GHz) (ppm/K) ReliabilityRemarks  1* — — — — Unsintered  2* — — — — Unsintered  3 10 6300 125 ◯ 4 11 6000 111 ◯  5 12 6300 135 ◯  6* 12 5500 133 X decreased Insulationreliability  7* 13 5300 136 X decreased Insulation reliability  8 155100 149 ◯  9 13 5100 149 ◯ 10 10 5700 149 X  11* 15 5300 672 ◯ degradedβ  12* 13 5100 660 ◯ degraded β 13 11 6000 136 ◯ 14 10 5800 128 ◯ 15 —5300 112 ◯ 16 12 6600 121 ◯ 17 12 5100 128 ◯  18* — — — — Unsintered 1911 6100 128 ◯  20* — — — — Unsintered 21 10 6000 126 ◯  22* — — — —Unsintered 23 10 6000 122 ◯  24* 12 5200 133 X decreased Insulationreliability 25 13 6400 132 ◯ 26 11 5400 112 ◯ 27  9 7900 112 ◯ 28 107800 114 ◯ 29 12 6400 133 ◯ 30 12 5500 139 ◯ 31 11 6800 122 ◯ 32 14 5400149 ◯ 33 12 5100 128 ◯ 34 11 6100 114 ◯ 35 10 5400 121 ◯ 36 11 6000 128◯ 37 10 6000 133 ◯ 38 12 5600 149 ◯  39* 12 5500 870 ◯ degraded β  40*12 5300 945 ◯ degraded β  41* 11 5300 135 X decreased Insulationreliability  42* 15 5100 136 X decreased Insulation reliability  43* — —— — Unvitrified  44* — — — — Unvitrified  45* 11 6300 125 X decreasedInsulation reliability  46* 13 5500 130 X decreased Insulationreliability  47* 10 5500 131 X decreased Insulation reliability  48* 145100 135 X decreased Insulation reliability

TABLE 5 Sample Qf β Insulation Number εr (GHz) (ppm/K) ReliabilityRemarks  49* 10 6300 720 ◯ degraded β  50* — — — — Unsintered 51 11 7200148 ◯ 52 10 5200 145 ◯ 53 8 7800 140 ◯  54* — — — — Unsintered 55 156800 114 ◯ 56 12 6200 126 ◯  57* 9 6000 175 ◯ degraded β  58* 9 5800 692X degraded β 59 9 8000 110 ◯ 60 15 7000 115 ◯ 61 8 6800 142 ◯ 62 9 5400132 ◯ 63 11 5800 138 ◯ 64 14 6300 135 ◯ 65 13 5700 128 ◯ 66 9 6100 125 ◯67 12 5400 132 ◯ 68 13 5700 130 ◯  69* 12 6500 135 X decreasedInsulation reliability 70 12 6400 146 ◯ 71 9 5400 146 ◯  72* 12 6000 146X decreased Insulation reliability  73* 10 6000 144 X decreasedInsulation reliability 74 12 7400 138 ◯ 75 10 5300 141 ◯  76* 12 5300140 X decreased Insulation reliability  77* 11 5300 175 ◯ degraded β 78* 12 5200 146 X decreased Insulation reliability 79 9 7200 147 ◯ 8013 5400 140 ◯ 81 9 6500 148 ◯  82* 9 6600 250 ◯ degraded β  83* 14 4600180 ◯ decreased Qf  84* 9 5200 195 ◯ degraded β  85* 12 4100 150 ◯decreased Qf  86* 12 5500 140 X decreased Insulation reliability  87* 105200 285 ◯ degraded β

In Tables 4 and 5, the sample numbers are marked with * for the samplesdetermined as rejected articles in this experimental example.

The following is determined from Tables 1 through 5.

First, the samples 1 to 48 shown in Tables 2 and 4 will be considered.For the samples 1 to 48, the glass G1 to G36 shown in Table 1 was allused for any of the samples. It is to be noted that the content of the“Glass” was made constant at “13 weight %” for all of the samples 1 to48.

The samples 1 and 2 were not sufficiently sintered. This is assumed tobe due to the use of the glass G1 with the Li₂O content lower than 0.3weight %.

The samples 6 and 7 underwent a decrease in insulation reliability. Thisis assumed to be due to the use of the glass G5 with the Li₂O contenthigher than 7.5 weight %.

The samples 11 and 12 underwent a decrease in temperature coefficient ofcapacitance β. This is assumed to be due to the use of the glass G8 withthe alkali-earth metal content lower than 44.0 weight %.

The sample 18 was not sufficiently sintered. This is assumed to be dueto the use of the glass G13 with the alkali-earth metal content higherthan 69.0 weight %.

The sample 20 was not sufficiently sintered. This is assumed to be dueto the use of the glass G15 with the B₂O₃ content lower than 10.0 weight%.

The sample 22 was not sufficiently sintered. This is assumed to be dueto the use of the glass G17 with the SiO₂ content higher than 30.0weight %.

The sample 24 underwent a decrease in insulation reliability. This isassumed to be due to the use of the glass G19 with the B₂O₃ contenthigher than 20.0 weight %.

The samples 39 and 40 underwent a decrease in temperature coefficient ofcapacitance β. This is assumed to be due to the use of the glass G32with the MgO content lower than 0.1 weight %.

The samples 41 and 42 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G33 with the MgOcontent higher than 5.5 weight %.

The samples 43 and 44 were not vitrified. This is assumed to be due tothe use of the glass G34 with the SiO₂ content lower than 14.2 weight %.

The samples 45 and 46 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G35 with the Al₂O₃content lower than 0.5 weight %.

The samples 47 and 48 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G36 with the Al₂O₃content higher than 4.0 weight %.

The samples 3 to 5, 8 to 10, 13 to 17, 19, 21, 23, and 25 to 38 shown inTables 2 and 4, except for the samples 1, 2, 6, 7, 11, 12, 18, 20, 22,24, and 39 to 48 mentioned above produced the results of Qf, β, andinsulation reliability.

This is assumed to be due to the use of any glass from among G2, G3, G4,G6, G7, G9, G10, G11, G12, G14, G16, G18, G20, G21, G22, G23, G24, G25,G26, G27, G28, G29, G30, and G31 which meet the conditions of: thealkali-earth metal content from 44.0 to 69.0 weight %; the SiO₂ contentfrom 14.2 to 30.0 weight %; the B₂O₃ content from 10.0 to 20.0 weight %;the Al₂O₃ content from 0.5 to 4.0 weight %; the Li₂O content from 0.3 to7.5 weight %; and the MgO content from 0.1 to 5.5 weight %.

As for ε_(r), all of the samples shown in Tables 2 and 4, except for thesamples with the evaluation results of “Unsintered” or “Unvitrified”,achieved a value of 15 or less.

Next, the samples 49 to 87 shown in Tables 3 and 5 will be considered.For the samples 49 to 87, the respective contents of the “Glass”, “FirstCeramic”, “Second Ceramic”, “MnO”, and “CuO” were varied while using theglass G22 shown as the “Glass” in Table 1.

The sample 49 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the BaO content lower than0.38 weight % in the second ceramic.

The sample 50 was not sufficiently sintered. This is assumed to be dueto the MnO content lower than 7.5 weight %.

The sample 54 was not sufficiently sintered. This is assumed to be dueto the glass content lower than 6 weight %.

The sample 57 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the Mg₂SiO₄ content higherthan 69.32 weight % as the first ceramic.

The sample 58 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the TiO₂ content lower than0.95 weight % in the second ceramic.

The sample 69 underwent a decrease in insulation reliability. This isassumed to be due to the Nd₂O₃ content higher than 9.5 weight % as RE₂O₃in the second ceramic.

The sample 72 underwent a decrease in insulation reliability. This isassumed to be due to the BaO content higher than 1.43 weight % in thesecond ceramic.

The sample 73 underwent a decrease in insulation reliability. This isassumed to be due to the glass content higher than 20 weight %.

The sample 76 underwent a decrease in insulation reliability. This isassumed to be due to the TiO₂ content higher than 6.75 weight % in thesecond ceramic.

The sample 77 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the MnO content higher than18.5 weight %.

The sample 78 underwent a decrease in insulation reliability. This isassumed to be due to the CuO content higher than 0.23 weight %.

The sample 82 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the Nd₂O₃ content lower than1.33 weight % as RE₂O₃ in the second ceramic.

The sample 83 underwent a decrease in Qf. This is assumed to be due tothe Mg₂SiO₄ content lower than 47.55 weight % as the first ceramic.

The sample 84 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the MgAl₂O₄ content higherthan 69.32 weight % as the first ceramic.

The sample 85 underwent a decrease in Qf. This is assumed to be due tothe MgAl₂O₄ content lower than 47.55 weight % as the first ceramic.

The sample 86 underwent a decrease in insulation reliability. This isassumed to be due to the Sm₂O₃ content higher than 9.5 weight % as RE₂O₃in the second ceramic.

The sample 87 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the Sm₂O₃ content lower than1.33 weight % as RE₂O₃ in the second ceramic.

The samples 51 to 53, 55, 56, 59 to 68, 70, 71, 74, 75, and 79 to 81shown in Tables 3 and 5, except for the samples 49, 50, 54, 57, 58, 69,72, 73, 76 to 78, and 82 to 87 mentioned above, have achieved favorableresults for Qf, β, and insulation reliability.

This is assumed to be due to the fact that the samples meet theconditions of: the first ceramic content from 47.55 to 69.32 weight %;the glass content from 6 to 20 weight %; the MnO content from 7.5 to18.5 weight %; the BaO content from 0.38 to 1.43 weight %; the RE₂O₃content from 1.33 to 9.5 weight %; the TiO₂ content from 0.95 to 6.75weight %; and the CuO content of 0.23 weight % or less.

As for ε_(r), all of the samples shown in Tables 3 and 5, except for thesamples with the evaluation results of “Unsintered”, achieved a value of15 or less.

It is to be noted that, while Nd₂O₃ and Sm₂O₃ were used as the RE₂O₃ inthe second ceramic in Experimental Example 1, it has been confirmed thatthe same tendency is shown even in the case of using other rare-earthelements.

Experimental Example 2

In Experimental Example 2, glass ceramics for the lowdielectric-constant ceramic layers were prepared as in ExperimentalExample 1, and in particular, influences on the low dielectric-constantglass ceramics, by the addition of a third ceramic including at leastone of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈, were examined.

Respective powders of spinel compound: MgAl₂O₄ and forsterite compound:Mg₂SiO₄, BaO, TiO₂, Nd₂O₃ as RE₂O₃, MnO, as well as CuO were prepared asin the case of Experimental Example 1.

Furthermore, in this Experimental Example 2, as shown in Table 6, MgCO₃,Al₂O₃, and SiO₂ were blended in predetermined proportions, and subjectedto calcination and wet grinding to prepare a powder of cordieritecompound: Mg₂Al₄Si₅O₁₈ as the third ceramic. Furthermore, likewise, asshown in Table 6, BaCO₃, Al₂O₃, and SiO2 were blended in predeterminedproportions, and subjected to calcination, and wet grinding to prepare apowder of celsian compound: BaAl₂Si₂O₃ as the third ceramic.

Next, respective powders of the glass shown in Table 1, MgAl₂O₄,Mg₂SiO₄, BaO, TiO₂, Nd₂O₃, MnO, CuO, Mg₂Al₄Si₅O₁₈, and BaAl₂Si₂O₈ wereblended so as to provide the compositions shown in Table 6. Then, thesepowders were mixed, and an organic solvent and a binder were then addedto the mixed powders to prepare slurry.

TABLE 6 First Ceramic Second Ceramic Third Ceramic Sample Glass (weight%) (weight %) MnO CuO (weight %) Number Number (weight %) MgAl₂O₄Mg₂SiO₄ BaO TiO₂ Nd₂O₃ (weight %) (weight %) Mg₂Al₄Si₅O₁₈ BaAl₂Si₂O₈ 101G22 10 0 68.92 0.8 3.8 5.4 11 0.08 0 0 102 G22 10 0 48.92 0.8 3.8 5.4 110.08 10 10 103 G3 10 0 66.92 0.8 3.8 5.4 11 0.08 2 0 104 G10 10 0 65.920.8 3.8 5.4 11 0.08 3 0 105 G18 10 0 58.92 0.8 3.8 5.4 11 0.08 10 0 106G22 10 0 48.92 0.8 3.8 5.4 11 0.08 20 0 107 G24 10 0 47.92 0.8 3.8 5.411 0.08 21 0 108 G3 10 0 66.92 0.8 3.8 5.4 11 0.08 0 2 109 G10 10 065.92 0.8 3.8 5.4 11 0.08 0 3 110 G18 10 0 58.92 0.8 3.8 5.4 11 0.08 010 111 G22 10 0 48.92 0.8 3.8 5.4 11 0.08 0 20 112 G24 10 0 47.92 0.83.8 5.4 11 0.08 0 21 113 G16 10 0 58.92 0.8 3.8 5.4 11 0.08 6 4

Thereafter, in the same manner as in the case of Experimental Example 1,samples were prepared, and evaluated for relative permittivity (ε_(r)),Qf, temperature coefficient of capacitance (β), insulation reliabilityas shown in Table 7. This experimental example was intended to obtaindielectric materials with lower ε_(r), such as ε_(r) of 8 or less.

TABLE 7 Sample Qf β Insulation Number εr (GHz) (ppm/K) Reliability 101 96500 100 ◯ 102 6 8678 74 ◯ 103 9 6915 93 ◯ 104 8 7186 72 ◯ 105 7 7322 64◯ 106 6 6915 62 ◯ 107 6 5559 54 ◯ 108 9 6915 85 ◯ 109 8 6915 72 ◯ 110 87186 66 ◯ 111 7 7322 64 ◯ 112 7 5288 54 ◯ 113 7 7186 67 ◯

The following is determined from Tables 6 and 7.

In comparison between the samples 102, 104 to 107, and 109 to 113containing 3 weight % or more of the third ceramic including at leastone of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈, and the samples 101, 103, and 108containing none of them, the former has achieved lower ε_(r), such as 8or less, and also achieved lower values for the temperature coefficientof capacitance β.

On the other hand, in the case of the samples 107 and 112 containingmore than 20 weight % of the third ceramic including at least one ofMg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈, decreases in Qf were observed.

Experimental Example 3

In Experimental Example 3, evaluations were made on glass ceramicsthemselves for high dielectric-constant ceramic layers.

In the same manner as in the case of Experimental Example 1, preparedwere respective powders of: a spinel compound: MgAl₂O₄ and a forsteritecompound: Mg₂SiO₄ as the first ceramic; BaO and TiO₂ as the secondceramic; Nd₂O₃ and Sm₂O₃ as RE₂O₃; MnO; as well as CuO. Furthermore, inthe same manner as in the case of Experimental Example 2, a powder ofcordierite compound: Mg₂Al₄Si₅O₁₈ and a powder of celsian compound:BaAl₂Si₂O₈ were prepared as the third ceramic.

Next, for the compositions shown in Tables 8 through 10, the respectivepowders of the glass shown in Table 1, MgAl₂O₄, Mg₂SiO₄, BaO, TiO₂,Nd₂O₃ and Sm₂O₃ as RE₂O₃, MnO, CuO, Mg₂Al₄Si₅O₁₈, and BaAl₂Si₂O₈ wereblended, and mixed, and an organic solvent and a binder were then addedthereto to prepare slurry.

TABLE 8 Second Ceramic First Ceramic (weight %) Sample Glass (weight %)BaO TiO₂ Nd₂O₃ MnO CuO Number Number (weight %) MgAl₂O₄ Mg₂SiO₄ (weight%) (weight %) (weight %) (weight %) (weight %) 201 G1 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 202 G1 11.5 27.5 0 4.05 19.15 26.85 10.85 0.1 203G2 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 204 G3 11.1 0 28.75 3.95 18.7526.6 10.75 0.1 205 G4 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 206 G5 11.10 28.75 3.95 18.75 26.6 10.75 0.1 207 G5 11.5 27.5 0 4.05 19.15 26.8510.85 0.1 208 G6 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 209 G6 11.5 27.50 4.05 19.15 26.85 10.85 0.1 210 G7 11.1 0 28.75 3.95 18.75 26.6 10.750.1 211 G8 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 212 G8 11.5 27.5 04.05 19.15 26.85 10.85 0.1 213 G9 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1214 G9 11.5 27.5 0 4.05 19.15 26.85 10.85 0.1 215 G10 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 216 G11 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 217G12 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 218 G13 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 219 G14 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 220G15 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 221 G16 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 222 G17 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 223G18 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 224 G19 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 225 G20 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 226G21 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 227 G22 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 228 G22 11.5 27.5 0 4.05 19.15 26.85 10.85 0.1 229G23 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 230 G23 11.5 27.5 0 4.0519.15 26.85 10.85 0.1 231 G24 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 232G25 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 233 G26 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 234 G27 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 235G28 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 236 G29 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 237 G30 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 238G31 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 239 G32 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 240 G32 11.5 27.5 0 4.05 19.15 26.85 10.85 0.1 241G33 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 242 G33 11.5 27.5 0 4.0519.15 26.85 10.85 0.1 243 G34 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 244G34 11.5 27.5 0 4.05 19.15 26.85 10.85 0.1 245 G35 11.1 0 28.75 3.9518.75 26.6 10.75 0.1 246 G35 11.5 27.5 0 4.05 19.15 26.85 10.85 0.1 247G36 11.1 0 28.75 3.95 18.75 26.6 10.75 0.1 248 G36 11.5 27.5 0 4.0519.15 26.85 10.85 0.1

TABLE 9 Second Ceramic First Ceramic (weight %) Third Ceramic SampleGlass (weight %) RE₂O₃ MnO CuO (weight %) Number Number (weight %)MgAl₂O₄ Mg₂SiO₄ BaO TiO₂ Nd₂O₃ Sm₂O₃ (weight %) (weight %) Mg₂Al₄Si₅O₁₈BaAl₂Si₂O₈ 249 G22 6.5 0 24.25 4.25 20.6 29.95 0 14.35 0.1 0 0 250 G22 70 25.25 4.2 20.55 29.65 0 13.25 0.1 0 0 251 G22 20 0 21.65 4 18.5 26.250 9.5 0.1 0 0 252 G22 21 0 20.65 4 18.5 26.25 0 9.5 0.1 0 0 253 G2210.75 0 14 4.1 19.15 28 0 16.5 0.5 7 0 254 G22 10.25 0 15.5 4.1 19.15 280 16.5 0.5 6 0 255 G22 15.75 0 47 2.25 9.5 13.2 0 11.8 0.5 0 0 256 G2216 0 48 2.25 9.5 13.2 0 10.55 0.5 0 0 257 G22 10.6 15.5 0 4.1 19.15 28 015.55 0.1 7 0 258 G22 15.05 47 0 2.25 9.5 13.2 0 12.5 0.5 0 0 259 G22 120 30.6 3.55 15.85 23.5 0 14 0.5 0 0 260 G22 8.5 0 33.55 3.75 16.55 24.050 13.5 0.1 0 0 261 G22 11.35 0 33.25 3.95 18.25 25.7 0 7 0.5 0 0 262 G228 0 34.05 3.75 16.55 24.05 0 13.5 0.1 0 0 263 G22 14.25 0 46 2 9.6513.45 0 14.55 0.1 0 0 264 G22 13.5 0 44.75 2.1 9.75 13.5 0 16.3 0.1 0 0265 G22 12.5 36.9 0 2.35 10.5 24.25 0 13.5 0 0 0 266 G22 11.25 0 30.83.75 16.55 24.05 0 13.5 0.1 0 0 267 G22 10.4 0 15.75 5.5 24.65 34.25 09.35 0.1 0 0 268 G22 12.75 0 46.5 2.25 9 13.25 0 16.15 0.1 0 0 269 G2212.95 0 45.7 2.25 9.5 13.3 0 15.8 0.5 0 0 270 G22 10.5 28.8 0 4.15 19.2527.2 0 10 0.1 0 0

TABLE 10 Second Ceramic First Ceramic (weight %) Third Ceramic SampleGlass (weight %) RE₂O₃ MnO CuO (weight %) Number Number (weight %)MgAl₂O₄ Mg₂SiO₄ BaO TiO₂ Nd₂O₃ Sm₂O₃ (weight %) (weight %) Mg₂Al₄Si₅O₁₈BaAl₂Si₂O₈ 271 G22 11.85 0 15.55 4.75 24.75 33.5 0 9.5 0.1 0 0 272 G2213 0 27.5 3.9 17.5 25.5 0 12.5 0.1 0 0 273 G22 17.25 0 38 2.45 11.8516.35 0 11.3 0.3 2.5 0 274 G22 10.25 0 16.05 4.95 25.5 34.65 0 8.5 0.1 00 275 G22 15 0 46.4 2.25 9.7 13.05 0 13.5 0.1 0 0 276 G22 14.3 0 45.252.55 10.35 13.2 0 14.25 0.1 0 0 277 G22 10.5 0 29.65 4.05 18.95 26.75 010 0.1 0 0 278 G22 14.25 0 45.5 2.45 10.25 0 13.2 14.25 0.1 0 0 279 G2211.5 0 16.25 5 24.35 0 34.75 8.05 0.1 0 0 280 G22 10.5 0 29.65 4.0518.95 0 26.75 10 0.1 0 0 281 G22 10 0 15.75 5.05 24.35 35.5 0 9.25 0.1 00 282 G22 18.9 0 33.55 3.55 15.75 23.25 0 4.5 0.5 0 0 283 G22 17.9 033.55 3.55 15.75 23.25 0 5.5 0.5 0 0 284 G22 9.25 0 25.2 3.7 16.65 24.20 20.5 0.5 0 0 285 G22 9.25 0 24.7 3.7 16.65 24.2 0 21 0.5 0 0 286 G2210 0 15.75 5.05 24.35 34.75 0 10 0.1 0 0 287 G22 12 0 17.25 4.75 22.2530.85 0 10.9 0.5 1.5 0 288 G22 10.5 0 33.1 2.4 10.4 24.5 0 11.5 0.1 7.50 289 G22 10.5 0 35.5 2.35 9.95 22.55 0 11.55 0.1 0 7.5 290 G22 10.85 015.75 5.2 24.5 34.25 0 9.35 0.1 0 0 291 G22 10.5 28.8 0 4.15 19.25 027.2 10 0.1 0 0 292 G22 11.5 0 32 2.4 10.45 24 0 11.55 0.1 8 0 293 G2210.75 0 27.55 3.85 18.25 25.55 0 12.85 1.2 0 0 294 G22 10.75 0 30 4.3520.25 27.65 0 6.5 0.5 0 0 295 G22 10.8 0 27.75 3.95 17.85 25.85 0 12.41.4 0 0

Thereafter, in the same manner as in the case of Experimental Example 1,samples were prepared, and evaluated for relative permittivity (ε_(r)),Qf, temperature coefficient of capacitance (β), insulation reliabilityas shown in Tables 11 and 12. This experimental example was intended toobtain dielectric materials with relatively high ε_(r), such as ε_(r) inthe range of 20 to 25. It is to be noted that, more strictly, thesamples with β in excess of 60 ppm/K in terms of absolute value weredetermined as rejected articles. In the columns of “InsulationReliability” of Tables 11 and 12, on the same test carried out as in thecase of Experimental Example 1, the samples are shown as “x” when thelog (IR [Ω]) after the test was less than 11, whereas the samples areshown as “o” when the log (IR [Ω]) is 11 or more.

It is to be noted that rejection reasons for the samples regarded asrejected articles in this experimental example are briefly described inthe columns of “Remarks” of Tables 11 and 12.

TABLE 11 Sample Qf β Insulation Number εr (GHz) (ppm/K) ReliabilityRemarks  201* — — — — Unsintered  202* — — — — Unsintered 203 20 8300 48◯ 204 23 9600 36 ◯ 205 24 9800 38 ◯  206* 24 9000 51 X decreasedInsulation reliability  207* 23 8600 50 X decreased Insulationreliability 208 23 8200 46 ◯ 209 23 7700 49 ◯ 210 22 8200 48 ◯  211* 224800 58 ◯ decreased Qf  212* 23 4600 56 ◯ decreased Qf 213 22 7700 46 ◯214 23 7600 45 ◯ 215 23 8900 41 ◯ 216 22 8800 40 ◯ 217 22 8700 48 ◯ 218* — — — — Unsintered 219 22 9400 42 ◯  220* — — — — Unsintered 22122 9400 39 ◯  222* — — — — Unsintered 223 22 9300 40 ◯  224* 23 8100 44X decreased Insulation reliability 225 23 9700 40 ◯ 226 22 9500 39 ◯ 22723 10600  35 ◯ 228 22 10200  42 ◯ 229 22 9700 38 ◯ 230 23 9200 36 ◯ 23122 9500 39 ◯ 232 24 7700 42 ◯ 233 23 8600 40 ◯ 234 24 8800 52 ◯ 235 207300 50 ◯ 236 22 8400 46 ◯ 237 23 9900 36 ◯ 238 21 7600 50 ◯  239* 207400 86 ◯ degraded β  240* 20 7200 88 ◯ degraded β  241* 21 9200 54 Xdecreased Insulation reliability  242* 22 8900 56 X decreased Insulationreliability  243* — — — — Unvitrified  244* — — — — Unvitrified  245* 216000 52 X decreased Insulation reliability  246* 22 6200 55 X decreasedInsulation reliability  267* 22 6100 58 X decreased Insulationreliability  248* 20 6200 55 X decreased Insulation reliability

TABLE 12 Sample Qf β Insulation Number εr (GHz) (ppm/K) ReliabilityRemarks  249* — — — — Unsintered 250 21 8200 53 ◯ 251 22 8600 48 ◯  252*22 7800 48 X decreased Insulation reliability  253* 25 5500 50 ◯decreased Qf 254 25 8200 42 ◯ 255 21 9000 54 ◯  256* 21 8300 74 ◯degraded β 257 24 7900 50 ◯ 258 22 9000 55 ◯ 259 23 9600 42 ◯ 260 219100 44 ◯ 261 23 9600 39 ◯ 262 21 9200 40 ◯  263* 16 7700 55 ◯ decreasedε_(r) 264 20 8100 52 ◯ 265 23 9600 47 ◯ 266 23 9800 45 ◯  267* 24 780050 X decreased Insulation reliability  268* 18 7900 46 ◯ decreased ε_(r)269 20 8400 46 ◯ 270 22 8000 46 ◯ 271 23 9400 48 ◯ 272 24 9300 48 ◯ 27324 7700 48 ◯  274* 23 8100 50 X decreased Insulation reliability  275*18 8000 55 ◯ decreased ε_(r) 276 20 9400 48 ◯ 277 24 10300  38 ◯ 278 219400 46 ◯ 279 23 9700 42 ◯ 280 23 9900 43 ◯  281* 23 9000 44 X decreasedInsulation reliability  282* — — — — Unsintered 283 20 9400 52 ◯ 284 228900 55 ◯  285* 22 4000 58 ◯ decreased Qf 286 24 8900 46 ◯ 287 22 870044 ◯ 288 21 8000 52 ◯ 289 21 7900 53 ◯ 290 20 9600 55 ◯ 291 23 9000 46 ◯ 292* 21 8000 68 ◯ degraded β 293 22 8400 50 ◯ 294 24 9300 40 ◯  295* 224500 50 ◯ decreased Qf

In Tables 11 and 12, the sample numbers are marked with * for thesamples determined as rejected articles in this experimental example.

The following is determined from Tables 8 through 12.

First, the samples 201 to 248 shown in Tables 8 and 11 will beconsidered.

For the samples 201 to 248, the glass G1 to G36 shown in Table 1 was allused for any of the samples. It is to be noted that the content of the“Glass” was adjusted to any of “11.1 weight %” and “11.5 weight %” forthe samples 201 to 248.

The samples 201 and 202 were not sufficiently sintered. This is assumedto be due to the use of the glass G1 with the Li₂O content lower than0.3 weight %.

The samples 206 and 207 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G5 with the Li₂Ocontent higher than 7.5 weight %.

The samples 211 and 212 underwent a decrease in Qf. This is assumed tobe due to the use of the glass G8 with the alkali-earth metal contentlower than 44.0 weight %.

The sample 218 was not sufficiently sintered. This is assumed to be dueto the use of the glass G13 with the alkali-earth metal content higherthan 69.0 weight %.

The sample 220 was not sufficiently sintered. This is assumed to be dueto the use of the glass G15 with the B₂O₃ content lower than 10.0 weight%.

The sample 222 was not sufficiently sintered. This is assumed to be dueto the use of the glass G17 with the SiO₂ content higher than 30.0weight %.

The sample 224 underwent a decrease in insulation reliability. This isassumed to be due to the use of the glass G19 with the B₂O₃ contenthigher than 20.0 weight %.

The sample 239 and 240 underwent a degradation in temperaturecoefficient of capacitance β. This is assumed to be due to the use ofthe glass G32 with the MgO content lower than 0.1 weight %.

The samples 241 and 242 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G33 with the MgOcontent higher than 5.5 weight %.

The samples 243 and 244 were not vitrified. This is assumed to be due tothe use of the glass G34 with the SiO₂ content lower than 14.2 weight %.

The samples 245 and 246 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G35 with the Al₂O₃content lower than 0.5 weight %.

The samples 247 and 248 underwent a decrease in insulation reliability.This is assumed to be due to the use of the glass G36 with the Al₂O₃content higher than 4.0 weight %.

The samples 203 to 205, 208 to 210, 213 to 217, 219, 221, 223, and 225to 238 shown in Tables 8 and 11, except for the samples 201, 202, 206,207, 211, 212, 218, 220, 222, 224, and 239 to 248 mentioned aboveproduced favorable results of: ε_(r) in the range of 20 to 25; Qf of7000 GHz or more, β of 60 ppm/K or less in terms of absolute value; andlog (IR [Ω]):11 or more in insulation reliability.

This is assumed to be due to the use of any glass from among G2, G3, G4,G6, G7, G9, G10, G11, G12, G14, G16, G18, G20, G21, G22, G23, G24, G25,G26, G27, G28, G29, G30, and G31 which meet the conditions of: thealkali-earth metal content from 44.0 to 69.0 weight %; the SiO₂ contentfrom 14.2 to 30.0 weight %; the B₂O₃ content from 10.0 to 20.0 weight %;the Al₂O₃ content from 0.5 to 4.0 weight %; the Li₂O content from 0.3 to7.5 weight %; and the MgO content from 0.1 to 5.5 weight %.

Next, the samples 249 to 295 shown in Tables 9 and 10 and Table 12 willbe considered. For the samples 249 to 295, the respective contents ofthe “Glass”, “First Ceramic”, “Second Ceramic”, “MnO”, “CuO”,“Mg₂Al₄Si₅O₁₈”, and “BaAl₂Si₂O₈” were varied while using the glass G22shown as the “Glass” in Table 1.

The sample 249 was not sufficiently sintered. This is assumed to be dueto the glass content lower than 7 weight %.

The sample 252 underwent a decrease in insulation reliability. This isassumed to be due to the glass content higher than 20 weight %.

The sample 253 underwent a decrease in Qf. This is assumed to be due tothe MgAl₂O₄ or Mg₂SiO₄ content lower than 15.5 weight % as the firstceramic.

The sample 256 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the MgAl₂O₄ or Mg₂SiO₄content higher than 47 weight % as the first ceramic.

The sample 263 was less than 20 in ε_(r). This is assumed to be due tothe BaO content lower than 2.1 weight % in the second ceramic.

The sample 267 underwent a decrease in insulation reliability. This isassumed to be due to the BaO content higher than 5.2 weight % in thesecond ceramic.

The sample 268 was less than 20 in ε_(r). This is assumed to be due tothe TiO₂ content lower than 9.5 weight % in the second ceramic.

The sample 274 underwent a decrease in insulation reliability. This isassumed to be due to the TiO₂ content higher than 24.75 weight % in thesecond ceramic.

The sample 275 was less than 20 in ε_(r). This is assumed to be due tothe Nd₂O₃ content lower than 13.2 weight % as RE₂O₃ in the secondceramic.

The sample 281 underwent a decrease in insulation reliability. This isassumed to be due to the Nd₂O₃ content higher than 34.75 weight % asRE₂O₃ in the second ceramic.

The sample 282 was not sufficiently sintered. This is assumed to be dueto the MnO content lower than 5.5 weight %.

The sample 285 underwent a decrease in Qf. This is assumed to be due tothe MnO content higher than 20.5 weight %.

The sample 292 underwent a degradation in temperature coefficient ofcapacitance β. This is assumed to be due to the third ceramic contenthigher than 7.5 weight %, which is composed of at least one ofMg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈

The sample 295 underwent a decrease in Qf. This is assumed to be due tothe CuO content higher than 1.2 weight %.

The samples 250, 251, 254, 255, 257 to 262, 264 to 266, 269 to 273, 276to 280, 283, 284, 286 to 291, 293, and 294 shown in Tables 9 and 10 andTable 12, except for the samples 249, 252, 253, 256, 263, 267, 268, 274,275, 281, 282, 285, 292, and 295 mentioned above, have achievedfavorable results such as: Qf of 7000 GHz or more, β of 60 ppm/K or lessin terms of absolute value; and insulation reliability of 11 or more inlog (IR [Ω]), in spite of ε_(r) in the range of 20 to 25.

This is assumed to be due to the fact that the samples meet theconditions of: the first ceramic content from 15.5 to 47 weight %; theglass content from 7 to 20 weight %; the MnO content from 5.5 to 20.5weight %; the BaO content from 2.1 to 5.2 weight %; the RE₂O₃ contentfrom 13.2 to 34.75 weight %; the TiO₂ content from 9.5 to 24.75 weight%; the CuO content of 1.2 weight % or less, as well as the third ceramiccontent of 7.5 weight % or less, which is composed of at least one ofMg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈.

It is to be noted that while Nd₂O₃ and Sm₂O₃ were used as the RE₂O₃ inthe second ceramic in Experimental Example 3, it has been confirmed thatthe same tendency is shown even in the case of using other rare-earthelements.

Experimental Example 4

In Experimental Example 4, for each of low dielectric-constant ceramiclayers and high dielectric-constant ceramic layers, the influence oncharacteristics, in particular, the influence on the relativepermittivity ε_(r) and temperature coefficient of capacitance β wasexamined in the case of a co-sintered body of the layers. FIGS. 6(A) and6(B) respectively show, in cross section, two types of co-sinteredbodies 71 and 72 prepared in this experimental example.

The co-sintered body 71 shown in FIG. 6(A) was structured to have a lowdielectric-constant ceramic layer 73 of 10 μm in thickness sandwichedbetween two high dielectric-constant ceramic layers 74 and 75 of 0.5 mmin thickness. Internal electrodes 76 and 77 were respectively formed soas to be partially opposed to each other between the lowdielectric-constant ceramic layer 73 and each of the highdielectric-constant ceramic layers 74 and 75, and external electrodes 78and 79 electrically connected to the internal electrodes 76 and 77respectively were formed on mutually opposed end surfaces.

The co-sintered body 72 shown in FIG. 6(B), reverse from the co-sinteredbody 71 shown in FIG. 6(A) in terms of positional relationship betweenthe low dielectric-constant ceramic layer and the highdielectric-constant ceramic layers, was structured to have a highdielectric-constant ceramic layer 80 of 10 μm in thickness sandwichedbetween two low dielectric-constant ceramic layers 81 and 82 of 0.5 mmin thickness. Internal electrodes 83 and 84 were respectively formed soas to be partially opposed to each other between the highdielectric-constant ceramic layer 80 and each of the lowdielectric-constant ceramic layers 81 and 82, and external electrodes 85and 86 electrically connected to the internal electrodes 83 and 84respectively were formed on mutually opposed end surfaces. The distancebetween the internal electrodes was 10 μm, and the electrode area was 4mm×4 mm.

The co-sintered bodies 71 and 72 were adjusted to 10 mm×10 mm in planardimension. In addition, the internal electrodes 76, 77, 83, and 84 aswell as the external electrodes 78, 79, 85, and 86 were formed byprinting a conductive paste containing Cu as a conductive component.

The co-sintered body 71 shown in FIG. 6(A) was used in the case ofevaluating the characteristics of co-sintered bodies with the lowdielectric-constant glass ceramic prepared in Experimental Examples 1and 2 described previously, whereas the co-sintered body 72 shown inFIG. 6(B) was used in the case of evaluating the characteristics ofco-sintered bodies with the high dielectric-constant glass ceramicprepared in Experimental Example 3.

For each of the low dielectric-constant ceramic layer 73 in theco-sintered body 71 and the high dielectric-constant ceramic layer 80 inthe co-sintered body 72, the determination of the relative permittivityε_(r) and temperature coefficient of capacitance β achieved resultsequivalent to those in each case of the low dielectric-constant glassceramic alone and high dielectric-constant glass ceramic alone.

More specifically, the relative permittivity ε_(r) was obtained from thefollowing formula with the electrostatic capacitance value at 1 MHz,which was measured with an LCR meter, as well as the area and distanceof the opposed electrodes.ε_(r)=(d×Cap)/(ε₀ ×S)

where d represents an interelectrode distance [m], S represents anopposed electrode area [m²], Cap represents electrostatic capacitance[F], and ε₀ represents a dielectric constant (8.854×10⁻¹² [F/]) invacuum.

In addition, the temperature coefficient of capacitance β was obtainedby the same method as in the case of Experimental Example 1.

It is to be noted that, although no particular evaluation was made onthe Qf, the Qf is also assumed to be equivalent to that in the case theglass ceramic alone, due to the fact that the relative permittivityε_(r) and temperature coefficient of capacitance β are equivalent asdescribed above.

Experimental Example 5

In Experimental Example 5, experiments were conducted to examine, in aco-sintered body of a low dielectric-constant ceramic layer and a highdielectric-constant ceramic layer, whether there are preferred rangesfor the ratio of G_(L)/G_(H) between the content G_(L) of glasscontained in the low dielectric-constant ceramic layer and the contentG_(H) of glass contained in the high dielectric-constant ceramic layer,as well as the ratio of M_(L)/M_(H) between the content M_(L) of MnOcontained in the low dielectric-constant ceramic layer and the contentM_(H) of MnO contained in the high dielectric-constant ceramic layer,and if any, which ranges are preferred.

In order to obtain samples with the ratios G_(L)/G_(H) and M_(L)/M_(H)varied variously, the low dielectric-constant glass ceramics shown inTable 3 with the sample numbers shown in the column “Sample Number forLow Dielectric-Constant Layer” of Table 13 were combined with the highdielectric-constant glass ceramics shown in Table 9 or 10 with thesample numbers shown in the column “High Dielectric-Constant SampleNumber” of Table 13 to prepare the co-sintered bodies 71 and 72 asrespectively shown in FIGS. 6(A) and 6(B).

In the respective columns “G_(L)/G_(H)” and “M_(L)/M_(H)” of Table 13,the ratio G_(L)/G_(H) and the M_(L)/M_(H) are each shown for thecombined low dielectric-constant glass ceramic and highdielectric-constant glass ceramic.

In this experimental example, the co-sintered body 71 shown in FIG. 6(A)was used to evaluate the low dielectric-constant glass ceramic forinsulation reliability, and the co-sintered body 72 shown in FIG. 6(B)was used to evaluate the high dielectric-constant glass ceramic forinsulation reliability.

For the evaluation of the insulation reliability, a test was carried outin which respective voltages of DC 200 V, 100 V, and 50 V were appliedfor 100 hours under a temperature of 150° C. between the externalelectrodes 78 and 79 of the co-sintered body 71 or between the externalelectrodes 85 and 86 of the co-sintered body 72. The insulationresistance was measured after the test, and the samples were determinedas rejected articles when the log (IR [Ω]) after this test was less than11.

The insulation reliability of the low dielectric-constant ceramic layerside is shown in the column “Reliability of Low Dielectric ConstantSide” of Table 13, whereas the insulation reliability of the highdielectric-constant ceramic layer side is shown in the column“Reliability of High Dielectric Constant Side” thereof, where the sampleis shown as “⊙” when the insulation resistance was not degraded even atthe applied voltage of 200 V, shown as “o” when the insulationresistance was degraded at 200 V, but not degraded at 100 V, or shown as“Δ” when the insulation resistance was degraded at 200 V and 100 V, butnot degraded at 50 V.

TABLE 13 Sample Sample Reliability Reliability Number Number of Low ofHigh for Low for High Dielectric Dielectric Sample Dielectric DielectricConstant Constant Number Constant Layer Constant Layer G_(L)/G_(H)M_(L)/M_(H) Side Side 301 64 261 0.53 2.14 Δ Δ 302 60 264 0.74 0.61 ◯ Δ303 55 284 1.30 0.49 ◯ Δ 304 62 261 1.76 2.57 ◯ Δ 305 62 294 1.86 2.77 ΔΔ 306 65 250 2.00 0.57 Δ Δ 307 71 262 1.94 0.70 Δ ◯ 308 51 251 0.60 1.42Δ ◯ 309 81 251 0.58 1.95 Δ ◯ 310 51 283 0.67 2.45 Δ Δ 311 53 272 1.150.96 ⊙ ⊙ 312 56 272 0.92 0.96 ⊙ ⊙ 313 59 272 1.00 1.20 ⊙ ⊙ 314 53 2771.43 1.20 ⊙ ⊙ 315 56 277 1.14 1.20 ⊙ ⊙ 316 59 277 1.24 1.50 ⊙ ⊙

In Table 13, first, when attention is focused on the “G_(L)/G_(H)”, thesamples 302 to 304 and 311 to 316 which meet the condition of0.74≦G_(L)/G_(H)≦1.76 have the evaluation of “o” or “⊙” achieved inregard to, in particular, “Reliability of Low Dielectric Constant Side”.

Next, when attention is focused on the “M_(L)/M_(H)”, the samples 307 to309 and 311 to 316 which meet the condition of 0.7≦M_(L)/M_(H)≦1.95 havethe evaluation of “o” or “⊙” achieved in regard to, in particular,“Reliability of High Dielectric Constant Side”.

Experimental Example 6

In Experimental Example 6, the influences of the ratio G_(L)/G_(H)between the glass contents and of the ratio M_(L)/M_(H) between the MnOcontents in a co-sintered body on the insulation reliability wereexamined as in the case of Experimental Example 5, and the warpageinhibiting effect was examined in the case of the lowdielectric-constant ceramic layer further containing a third ceramicincluding at least one of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈.

In this Experimental Example 6, in order to obtain samples with theratio G_(L)/G_(H) and ratio M_(L)/M_(H) varied variously, the lowdielectric-constant glass ceramics shown in Table 6 with the samplenumbers shown in the column “Sample Number for Low Dielectric-ConstantLayer” of Table 14 were combined with the high dielectric-constant glassceramics shown in Table 9 or 10 with the sample numbers shown in thecolumn “High Dielectric-Constant Sample Number” of Table 14 to preparethe co-sintered bodies 71 and 72 as respectively shown in FIGS. 6(A) and6(B).

Next, in the same manner as in the case of Experimental Example 5, the“Reliability of Low Dielectric Constant Side” and “Reliability of HighDielectric Constant Side” were evaluated as shown in Table 14.

In this Experimental Example 6, furthermore, “Warpage” was evaluated asshown in Table 14.

As for the “Warpage”, a composite substrate of 50 mm×50 mm in planardimension and 1 mm in thickness was prepared by stacking a lowdielectric-constant ceramic layer of 0.5 mm in thickness and a highdielectric-constant ceramic layer of 0.5 mm in thickness, and placed ona surface plate to measure the level of the highest point, and the valueobtained by subtracting the thickness of the composite substrate fromthe level was determined as a warpage amount. The samples with a warpageamount of 0.1 mm or less were determined as accepted articles, and areshown as “0” in the column “Warpage” of Table 14, whereas the sampleswith the warpage amount in excess of 0.1 mm were determined as rejectedarticles, and are shown as “x” in the same column.

TABLE 14 Sample Sample Reliability Reliability Number Number of Low ofHigh for Low for High Dielectric Dielectric Sample Dielectric DielectricConstant Constant Number Constant Layer Constant Layer G_(L)/G_(H)M_(L)/M_(H) Side Side Warpage 401 101 277 1.24 1.43 ⊙ ⊙ X 402 102 2771.24 1.43 ◯ ◯ ◯ 403 103 259 1.08 1.07 ◯ ◯ X 404 104 260 1.53 1.11 ◯ ◯ ◯405 105 266 1.16 1.11 ◯ ◯ ◯ 406 106 272 1.00 1.20 ◯ ◯ ◯ 407 107 287 1.081.38 ◯ ◯ X 408 108 259 1.08 1.07 ◯ ◯ X 409 109 260 1.53 1.11 ◯ ◯ ◯ 410110 266 1.16 1.11 ◯ ◯ ◯ 411 111 272 1.00 1.20 ◯ ◯ ◯ 412 112 287 1.081.38 ◯ ◯ X 413 113 277 1.24 1.50 ◯ ◯ ◯

In regard to the “Reliability of Low Dielectric Constant Side” and“Reliability of High Dielectric Constant Side” in Table 14, a tendencyis indicated which is similar to that in the case of ExperimentalExample 5.

More specifically, in Table 14, first, when attention is focused on the“G_(L)/G_(H)”, the samples 401 to 413 all meet the condition of0.74≦G_(L)/G_(H)≦1.76, and have the evaluation of “o” or “⊙” achieved inregard to the “Reliability of Low Dielectric Constant Side”.

Next, when attention is focused on the “M_(L)/M_(H)”, the samples 401 to413 all meet the condition of 0.7≦M_(L)/M_(H)≦1.95, and have theevaluation of “◯” or “⊙” achieved in regard to “Reliability of HighDielectric Constant Side”.

Furthermore, the samples 506 to 511 which meet both of the conditions1.0≦G_(L)/G_(H)≦2.0 and 1.5≦M_(L)/M_(H)≦3.6 have the evaluation of “⊙”achieved in regard to both “Reliability of Low Dielectric Constant Side”and “Reliability of High Dielectric Constant Side”.

Next, as for the “Warpage”, the samples 402, 404 to 406, 409 to 411, and413 have the evaluation of “◯” achieved, which use the lowdielectric-constant glass ceramics according to the samples 102, 104 to106, 109 to 111, and 113 further containing 3 to 20 weight % of thethird ceramic including at least one of Mg₂Al₂Si₅O₁₅ and BaAl₂Si₂O₈ inthe “Low Dielectric-Constant Layer”.

Experimental Example 7

In Experimental Example 7, the influences of the ratio G_(L)/G_(H)between the glass contents and of the ratio M_(L)/M_(H) between the MnOcontents in a co-sintered body on the insulation reliability wereexamined as in the case of Experimental Example 6, and the warpageinhibiting effect was examined in the case of the lowdielectric-constant ceramic layer further containing a third ceramicincluding at least one of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈.

Furthermore, in the experimental example, the influences of thedifference (C_(L)−C_(H)) between the content C_(L) of the third ceramiccontained in the low dielectric-constant ceramic layer and the contentC_(H) of the third ceramic contained in the high dielectric-constantceramic layer on insulation reliability and warpage were examined in thecase of the high dielectric-constant ceramic layer containing the thirdceramic.

In this Experimental Example 7, in order to obtain samples with theratio G_(L)/G_(H) and ratio M_(L)/M_(H) as well as difference(C_(L)−C_(H)) varied variously, the low dielectric-constant glassceramics shown in Table 6 with the sample numbers shown in the column“Sample Number for Low Dielectric-Constant Layer” of Table 15 werecombined with the high dielectric-constant glass ceramics shown in Table10 with the sample numbers shown in the column “High Dielectric-ConstantSample Number” of Table 15 to prepare the co-sintered bodies 71 and 72respectively as shown in FIGS. 6(A) and 6(B).

Next, in the same manner as in the case of Experimental Example 5, the“Reliability of Low Dielectric Constant Side” and “Reliability of HighDielectric Constant Side” were evaluated as shown in Table 15.

In addition, in the same manner as in the case of Experimental Example6, “Warpage” was evaluated as shown in Table 15.

TABLE 15 Sample Sample Reliability Reliability Number Number of Low ofHigh for Low for High Dielectric Dielectric Sample Dielectric DielectricC_(L) − C_(H) Constant Constant Number Constant Layer Constant Layer(weight %) G_(L)/G_(H) M_(L)/M_(H) Side Side Warpage 501 104 287 1.51.08 1.38 ⊙ ⊙ X 502 104 289 −4.5 1.24 1.30 ⊙ ⊙ X 503 109 287 1.5 1.081.38 ⊙ ⊙ X 504 109 289 −4.5 1.24 1.30 ⊙ ⊙ X 505 105 273 7.5 0.75 1.33 ⊙⊙ ◯ 506 105 288 2.5 1.24 1.30 ⊙ ⊙ ◯ 507 105 289 2.5 1.24 1.30 ⊙ ⊙ ◯ 508110 287 8.5 1.08 1.38 ⊙ ⊙ ◯ 509 110 288 2.5 1.24 1.30 ⊙ ⊙ ◯ 510 110 2892.5 1.24 1.30 ⊙ ⊙ ◯ 511 106 289 12.5 1.24 1.30 ⊙ ⊙ ◯ 512 111 287 18.51.08 1.38 ⊙ ⊙ ◯ 513 111 289 12.5 1.24 1.30 ⊙ ⊙ ◯

In Table 15, the samples 501 to 513 all meet both of the conditions0.74≦G_(L)/G_(H)≦1.76 and 1.5≦M_(L)/M_(H)≦3.6, and have the evaluationof “⊙” achieved in regard to both “Reliability of Low DielectricConstant Side” and “Reliability of High Dielectric Constant Side”.

In this regard, the samples 273, 287, 288, and 289 shown in the columnof “Sample Number for High Dielectric Constant Layer”, for use in thesamples 501 to 513 were each adapted to contain the third ceramic in therange of 1 to 7.5 weight %.

Next, when attention is focused on the “C_(L)−C_(H)”, the difference is2.5 weight % or more in the samples 505 to 513. As a result, the samples505 to 513 have the evaluation of “◯” in regard to “Warpage”. On theother hand, the samples 501 to 504 with the “C_(L)−C_(H)” less than 2.5weight % have the evaluation of “x” made in regard to “Warpage”.

DESCRIPTION OF REFERENCE SYMBOLS

-   -   1 ceramic multilayer module    -   2 multilayer ceramic substrate    -   3, 73, 81, 82 low dielectric-constant ceramic layer    -   4, 74, 75, 80 high dielectric-constant ceramic layer    -   21 LC filter    -   23 component body    -   28 to 32, 35 to 40 low dielectric-constant ceramic layer    -   33, 34 high dielectric-constant ceramic layer    -   71, 72 co-sintered body

The invention claimed is:
 1. A composite laminated ceramic electroniccomponent comprising: a first dielectric-constant ceramic layer and asecond dielectric-constant ceramic layer that are stacked, the firstdielectric-constant ceramic layer having a lower dielectric constantthan the second dielectric-constant ceramic layer, wherein the firstdielectric-constant ceramic layer and the second dielectric-constantceramic layer each comprises: a glass ceramic containing: (1) a firstceramic comprising at least one of MgAl₂O₄ and Mg₂SiO₄; (2) a secondceramic including BaO, RE₂O₃, and TiO₂; (3) glass containing each of44.0 to 69.0 weight % of RO, 14.2 to 30.0 weight % of SiO₂, 10.0 to 20.0weight % of B₂O₃, 0.5 to 4.0 weight % of Al₂O₃, 0.3 to 7.5 weight % ofLi₂O, and 0.1 to 5.5 weight % of MgO; and (4) MnO, wherein RE is arare-earth element, wherein R is at least one alkali-earth metalselected from Ba, Ca, and Sr, wherein the first dielectric-constantceramic layer: contains 47.55 to 69.32 weight % of the first ceramic;contains 6 to 20 weight % of the glass; contains 7.5 to 18.5 weight % ofthe MnO; contains, as the second ceramic, each of 0.38 to 1.43 weight %of BaO, 1.33 to 9.5 weight % of RE₂O₃, and 0.95 to 6.75 weight % ofTiO₂; and has a relative permittivity of 15 or less, and wherein thesecond dielectric-constant ceramic layer: contains 15.5 to 47 weight %of the first ceramic; contains 7 to 20 weight % of the glass; contains5.5 to 20.5 weight % of the MnO; contains, as the second ceramic, eachof 2.1 to 5.2 weight % of BaO, 13.2 to 34.75 weight % of RE₂O₃; and 9.5to 24.75 weight % of TiO₂; and has a relative permittivity of 20 or moreand 25 or less.
 2. The composite laminated ceramic electronic componentaccording to claim 1, wherein a content G_(L) of the glass contained inthe first dielectric-constant ceramic layer and a content G_(H) of theglass contained in the second dielectric-constant ceramic layer meet acondition of 0.74≦G_(L)/G_(H)≦1.76.
 3. The composite laminated ceramicelectronic component according to claim 1, wherein a content M_(L) ofthe MnO contained in the first dielectric-constant ceramic layer and acontent M_(H) of the MnO contained in the second dielectric-constantceramic layer meet a condition of 0.7≦G_(L)/G_(H)≦1.95.
 4. The compositelaminated ceramic electronic component according to claim 1, wherein acontent G_(L) of the glass contained in the first dielectric-constantceramic layer and a content G_(H) of the glass contained in the seconddielectric-constant ceramic layer meet a condition of0.74≦G_(L)/G_(H)≦1.76, and a content M_(L) of the MnO contained in thefirst dielectric-constant ceramic layer and a content M_(H) of the MnOcontained in the second dielectric-constant ceramic layer meet acondition of 0.7≦M_(L)/M_(H)≦1.95.
 5. The composite laminated ceramicelectronic component according to claim 1, wherein the firstdielectric-constant ceramic layer further contains 3 to 20 weight % of athird ceramic including at least one of Mg₂Al₄Si₅O₁₈ and BaAl₂Si₂O₈. 6.The composite laminated ceramic electronic component according toaccording to claim 5, wherein the second dielectric-constant ceramiclayer contains 1 to 7.5 weight % of the third ceramic, and a differencebetween a content C_(L) of the third ceramic contained in the firstdielectric-constant ceramic layer and a content C_(H) of the thirdceramic contained in the second dielectric-constant ceramic layer is 2.5weight % or more.
 7. The composite laminated ceramic electroniccomponent according to claim 1, wherein the first dielectric-constantceramic layer further contains 0.23 weight % or less of CuO.
 8. Thecomposite laminated ceramic electronic component according to claim 7,wherein the second dielectric-constant ceramic layer further contains1.2 weight % or less of CuO.
 9. The composite laminated ceramicelectronic component according to claim 1, wherein the seconddielectric-constant ceramic layer further contains 1.2 weight % or lessof CuO.
 10. The composite laminated ceramic electronic componentaccording to claim 1, wherein the first dielectric-constant ceramiclayer has a temperature coefficient of capacitance of 150 ppm/K or less.11. The composite laminated ceramic electronic component according toclaim 10, wherein the second dielectric-constant ceramic layer has atemperature coefficient of capacitance of 60 ppm/K or less.
 12. Thecomposite laminated ceramic electronic component according to claim 1,wherein the second dielectric-constant ceramic layer has a temperaturecoefficient of capacitance of 60 ppm/K or less.